Process of treating matters in fusion.



No. 754,555. PATENTBD MAR. 15, 1904.

.1. L. HULIN. PRooEss 0F TREATING MATTERS 1N FUSION. AIPLIGATION FILEDDEO. 29. 1902.

N0 MODEL. 3 SHEETS-SHEET 1.

INVENTURf:

WITNEEEELE f @M4 m ATT DIRYNEYE PATENTED MAR. 15, 1904.

P. L. HULIN.

PROCESS OP TREATING MATTERS IN FUSION.

APPLICATION FILED DEO. 29. 1902.

3 SHEETS-SHEET 2.

NO MODES.

INVENTUR ATTDRNEYE PATENTES-MAR. 15, 1904.

P. L. HULIN.

PROCESS 0F TRBATING MATTERS 1N FUSION.

APPLICATION FILED DEO. 29, 1902.

3 SHEETS-SHEET 3.

NO MODEL.

VVITNEEEEE:

ATTDRNEYE.

' phids,

` which it cannot be readilyV or uniformly disand similar compounds ofchromium, many UNITED STATES atented maren i5, 1904.

PROCESS OF TREATING MATTERS IN FUSION.

SPEGFICATION forming part of Letters Patent No.

Application iled December 29, 1902.

To al?, `whom, it may concern.-

Be it known that I, PAUL LON HULIN, engineer, of Clavaux, par Riouproux,Isere, Re public of France, have invented aProcess for Treating Mattersin Fusion, of which the fol lowing is a full, clear, and exactdescription.V

This invention relates to a process for effecting in a practical andadvantageous manner the incorporation of sodium or alkaline compoundswith metals or matters in fusion on which it is desired that thealkalies should react.

The commercial utility of a practical proc-v ess of incorporating sodiumwith molten matters is especially evidenced by the following examples:

First. It would be of great advantage in metallurgy to be able to causesodium or alkaline compounds to react readily and effectually within themass of such metals as cast-iron, steel, nickel, copper, &c., in fusion,as especially sodium and also certain of its derivatives are the bestpurifying agents for such metals. The alkalies destroy or eliminate in astate of highly fluid slag the oxide, phosarsenids, &c., contained inordinary metals, which may thus be obtained in a very pure condition.

Second. It would even be advantageous to be able to conveniently alloysodium with aluminium or with zinc or other metals in solved.For-instance, if zinc and Vsodium be heated together difliculties arisein obtaining l a homogeneous alloy. A

Third. It is also necessary to be able to effect on a large scalewithout danger and with good economical results the reduction of certainchlorids, luorids, and other compounds in igneous fusion by means ofsodium, which liberates the metal' byA combining with the chlorin `orthe fluorin, ter-for example, chlorid of magnesium, iiuorid ofaluminium,

ganese, &c., and even chloride of calcium and barium when operating inpresence of a metal, such as zinc, capable of absorbing calcium orbarium. It is known that by the reaction of sodium with these matters infusion there is 754,566, dated march 15, 1904.

Serial No. 138,926. (No specimens.)

sodium, and, on the other hand, metallic magnesium, aluminium, chromium,or manganese.

With chlorids of calcium or barium in presence of zinc anA alloy of zincand calcium or of zinc and barium, &c., is obtained. These operationsabove referred to have not become commercially available on account ofthe diiiculties attendant on the employment of sodium or alkalinecompounds by known methods.

Fourth. There are-many other chemical or metallurgical reactionsrequiring some practical method of employing sodium in order to renderthem available commercially. So far as I am aware it has been usualhitherto to employ sodium in lumpsthat is to say, in compactmasses-which were, moreover, mechanically inert at the moment ofentering into reaction, Under these conditions the properties of sodiumare incompatible with its use for the operations in question.

The lightness of sodium and of alkaline 'compounds prevents them frompenetrating into or remaining in the midst of the molten mass, whiletheir volatility at the temperatures of the operation causes occasionalblowing up or overflowing of the molten matters. Moreover, the chemicalactivity of these alkaline compounds in a oatng condition destroyed theapparatus and rendered the operations diflicult and often impracticable.

The present invention has for its object to practically and economicallyeect the incorporation of sodium and alkaline compounds lighter than thebath of molten matter and which are at the same time either volatile orcorrosive or diiiicult to use at the necessary temperatures with thenecessary degree of safety. My invention therefore provides a practicalmethod of effecting on a commercial scale the metallurgical or chemicaloperations hereinbefore referred to.

In order to simplify the description, the term bath, will hereinafter befrequently applied to the metals and matters in fusion subjected toalkaline treatment, and I desire it to be understood that instead ofsodium I may employ as equivalents thereof the readilyfusible alkalinecompounds, such as caustic alkalies, alkaline nitrates, &c.

The process consists, essentially,in introduc- IOO ing the sodium intothe bath in a liquid state and in the form of a fine jet, which iscausedv to penetrate the mass in a downward direction (perpendicularlyor obliquely)under the action of high pressure. By these means thealkali metal acts upon the mass by mechanical action derived from thepowerful downwardly-penetrative movement of the jet of liquid sodium.This mechanical penetrative action which is `exerted in opposition tothe buoyant or ascensional force tends to cause. the sodium toescape,and thus abreaking up and an intimate incorporation of the molecules iseffected. These mechanical eiects thus cooperate with the chemicalaction and'y enable it to attain its maximum of eciency. My process isthus characterized by the downwardly-directed penetrative movement of astream-of sodium as a means of causing it to exert chemical action upondense matters in fusion.

Reference is to be had to the accompanying drawings, in which- Figure 1is a sectional elevation of an apparatus suitable for carrying out lmyinvention. Figs. 2-and 3 are similar views4 of two other forms ofapparatus. Figs. 4, .5, and 6 are sectional elevations of thesodium-containers used in conjunction with the apparatus shown in Figs.1, 2, and 3, respectively.

A is any suitable container for the molten bath, and B is the bath infusion (metal or compound) into which the sodium is to be injected forpurposes of purication, alloying, or decomposition. C is a vesselcontaining liquid sodium under pressure.

D, Fig. 1, and E, Figs. 2 and 3, represent a twyer or small-bored nozzlegiving passage .to a fine jetof sodium which under the high pressureapplied at F in the vessel C is projected downward into the bath at asufficientlyhigh initial velocity to insure its penetration. The jet onstriking the molten material becomes divided into very minute globules,4which owing to the force of the jet are stirred into and becomedispersed through the mass of the bath, whereby the sodium becomesabsorbed and utilized in an eicient manner., As the sodium is not in theform of lumps nor locally massed in the bath, but is, on the contrary,in a high state of dispersion and tenuity, the reaction is performedwithout danger, and the-destructive effect on the apparatus is re ducedto a minimum. Should the temperature cause volatilization of the sodium,(as in purifying molten steel,) this distillation being distributeduniformly it Will be easy to confine the mass in ebullition. y

I designate as scouring the operation hereinbefore described, whichconsists in introducing sodium into baths in fusion in the form of aliquid jet having the velocity necessary for its downward penetrationand rapid dispersion. This appellationhas reference to the mostimportant application of the process Amusee at present foreseen-viz.,the purification of metals on leaving the melting-furnaces.

The apparatus devised for practically effecting the incorporation ofsodium in baths in fusion present some new and characteristic featuresin view of the process for which they are-designed. These apparatus(separately represented in Figs. 4, 5, and) I denominate scourers Theyare by their nature independent of any vessel, ladle, melting-pot,crucible, or furnace, &c., in which the baths to be treated arecontained, as likewise the natureof the moltenmatters to be subjected tothe action of the sodium jet, the twyers being of course adapted to thekind of work to i 'be performed. In practice this independence isrelative, as the scourers may be more or less adapted or fixed to thevessels containing the baths at the time of performing the operation;but they would always be made removable, an especial feature being thefact that they may be removed and be charged and prepared at a ,distancefrom the ybaths of molten material to be operated on.

Figs. 4c, 5, and 6 represent the principal varieties of the apparatus.C, Figs. l to 6, is a metallic container hermetically closed and capableof withstanding high pressures, into which the melted sodium H isvintroduced -through the orifice closed by a screw-plug G,

a sufficient space F above the sodium being left for fluid underpressure, such as a suitable gas, vapor, or liquid. This compressedvfluid which supplies the motive force may be supplied to F through a'pipe f from an outside reservoir or compressor, .with which it mayremain in communication duringthe discharge of the'sodium. This externalsource of supply is not, however, necessary, and as it is inconvenientwhen performing the opera-- tion it may be dispensed with by adoptingwhat I term a charged scourer, which fulfils all requirements and iseasily manipulated. For this purpose the chamber F is made' of suchcapacity that the supply of compressed gas or vapor contained issuiiicient to insure the discharge of' the sodium under properconditions. The compressed gas is obtained from any suitable source andis introduced through the valve J by means of a connecting-pipe f, whichwhen the pressure is established is disconnected after shutting ascrew-valve g, as shown in Fig. 2. The gas employed may be of variouskinds-viz., nitrogen, carbonio oxid, carbonio acid, poor gas, or evenordinary air-to the exclusion of ammoniacal gas, steam, alcohol, andothers capable of readily combining with sodium. l

To avoid the employment of a special supply of compressed gas, and thusstill further simplify the apparatus, I may substitute for the gas asuitable volatile liquid, `.by which pressure would be generated at themoment of use when the'vessel is heated for the pur- TOO IlO'

pose of melting the sodium. For this lpur- -volatile liquid capable ofproducing a high pressure is introduced at G or K, and the plug is thenhermetically closed. The vessel thus charged is prepared for use byheating the container C in orderto melt the sodium and volatilize thebenzene, thereby generating high pressure, which, acting upon thesodium, insures its discharge at ahigh initial velocity.

The apparatus also comprises as a distinctive feature a discharge nozzleor tube for delivering the sodium in the.form of a fine jet of liquid,consistingof and herein referred to as the twyer D, Fig. l, or E inFigs. 2 and 3. It may be of three diiferent forms (shown in these threefigures) and is made of iron or steel, copper, bronze, or nickel, or ofother sufficiently strong material, either bare or cased, either Awhollyor partly in a sheath of refractory material, such as that shown at L.It consists, essentially, of a strong tube D or E, firmly connected tothe lower end of the container C. Itsbore is very small-that is to say,from one to five millimeters only, for instance; but this dimension may,however, vary according to circumstances and is in no Way limited. TheWalls of the tWyer-tube should be made comparatively thick. Thearrangement shown in Fig. l is-characterized by the disposition ofthetwyer D at a distancefabove the bath B, so that the jet of sodium M iscaused to traverse the intervening space by its momentum and penetratethe bath by the effect of a ballistic action. This form of apparatus ismore particularly employed for treating metals or matters in fusion,which could not conveniently be brought into c'ontact with the twyer, orwhen it is desired to avoid changing it, or where the products of theoperation are liable to be soiled. This arrangement is suited for thetreatment of baths of which the level does not vary much during theoperation, and it is particularly employedin the preparation of alloys.

As an example of working I will describe the preparation of an alloy ofsodium and aluminium. I take a scourer with a short twyer, such as C D,Figs. l and 4, close the twyer by means of an aluminium cap N, in-

- troduce melted sodium at the orifice G, leavingthe necessary spaceabove the liquid to contain the motive fluid F. The orifice is thenclosed by the stopper, and the elastic pressure in the container is thengenerated by one of the methods hereinbefore specified. The vessel C Dis then uniformly heated throughout to a temperature higher than thefusing-point of sodium-viz., to about 150O c entigrade-` and it is thenbrought over the bath B with.

the twyer slightly raised above the surface in a vertical or inclinedposition. The crucibleA of suitable material contains melted aluminiumin a very fluid condition-that is to say,

.of the jet.

heated to a temperature above its fusing-point. When the scourer vesselis in position over the Crucible A, the cap N, Fig. 4, is melted offeither by a jet of flame or by a highlyheated block of iron applied toit or other- Wise.` The twyer being thus uncapped the jet of sodium isprojected forcibly into the midst of the aluminium, withwhich it becomesalloyed as a result of the energetic stirring and dispersion produced bythe penetrative effect If the twyer were closed by a soldered capsule,its unstoppage would be similarly effected. It will be understood thatthe crucible A may have a cover with a hole in it for the twyer andmaking a more or less tight joint. The details and accessories of thiskind would vary according to circumstances, and being outside the scopeof the process itself they are omitted from the present description. Bya similar operation and with the same apparatus an` alloyof zinc andcalcium may be prepared. In this case 4the crucible A, which may beplaced over a furnace, would contain zinc in thoroughlyv moltencondition covered With a layer of molten chlorid of calcium. Theoperation is conducted as before, the jet of sodium being made totraverse the chlorid of calcium and carry it along with it down into themass of zinc, the intimate incorporation due to the penetrative actionof the jet resulting in the reduction of the chlorid of calcium by thesodium and the formation of an alloy of zinc and calcium, according tothe well-known reaction. By means of a similar operation chromium,titanium, tungsten, molybdenum, vanadium, and other. metals may beincorporated with cast iron or steel, nickel, copper, &e., in fusion. Itis only necessary to cover the cast iron, steel, or copper, ac., with alayer of a molten compound of chromium, titanium, &c., reducible bysodium, and to cause a jet of molten sodium to traverse the V,mass in adownward direction, whereby to effect simultaneously the reduction ofthe compound and the incorporation of the chromium, titanium, or othermetals to be alloyed with the bath.

IOO

For the production of magnesium the crucible A is charged withcarnallite in igneous fusion and a jet of sodium is then projected, asbefore described, into the bath, through which it becomes dispersed, theresulting decomposition thus producing magnesium under much moreadvantageous conditions than when sodium in inert lumps-is employed. Byoperating in a similar manner with a mixture of two or more suitablemetallic salts themetals which form the bases of the salts may bealloyed. Thus by injecting, as before described, a jet of liquid sodiuminto a suitable mixture containing chlorid of magnesium and fluorid ofaluminium in fusion an alloyv of magnesium and aluminium will beobtained. In this manner all sorts of alloys may be produced,particularly those of the alkali-earth metals, which are diiicultlyobtainable in a free state. The same apparatus C D, Fig. 1,

' arranged and operating'in a similar manner .very high pressurepenetrates the molten srs e, reaches the end of the twyer, whichrapidlyf metal., combines with the impurities, and carries them oifupward and out of the metal either in the form of slag or fumes.

The apparatus represented in Fig. 2-is characterized by the length oftwyer E and is adapted for use in purifying ordinary metals in largemasses, especially at the moment of Itapping off into the v"ladle fromthe blastfurnace, converter, cupola, or other furnace or producingapparatus. This long twyer is employed in applying the process to'thetreatment of baths of which the level gradually rises. It alsosimplifies 'the operation by dispensing with the necessity of having tounseal the end of the twyer, which in this instance opens automaticallyat the proper moment, as hereinafter explained. As an example of theoperation, I will describe the final purification of a bath of steel B,being the last fusion run -from the Bessemer or Thomas converter orSiemens-Martin furnace into a ladle. A, Fig.

2. The vessel C E ischarged with sodiumY and is put under pressure andprepared as hereinbefore described. The twyer E is formed of a thickiron orsteel tube having albore of about three millimeters and whoseextremity O is closed either by compression or by forging or welding orby means of a screw-cap. The twyer should belong enough to reach nearlyto the bottom of ladle A, the container C being supported well above theladle. The apparatus after having been charged, heated throughout, andputlunder pressure is placed in the position represented in Fig. 2 withthe twyer dipping into the ladle and there rmly secured by any suitablemechanical means. Molten steel is then run into the ladle, in which itgradually rises and soon becomes fused at the pointof contact inconsequence of the high temperature of the inflowing steel.

' through the twyer is discharged in the form of a fine rapid jet, whichquickly penetrates the mass and becomes disseminated through- -out andcomes into intimatecontact with the oxids, sulids, &c., under .the mostfavorable conditions for their conversion into light fusible or volatileslag, which becomes com- The-sodium finding an issue simplifies theworking of the process of purification of metals on a large scale,inasmuch as the operation is thereby rendered automatic and safe, nowork being required to be done during the running-in of the metals, and,in

short, affords a complete and satisfactory nickel or copper as it leavesthe meltingfurnace; but it would be preferable to employ a nickel twyerin the one case and a copper twyer in the other.

Fig. 3 represents another arrangement of twyer, consisting of the samemetal tube E, closed at the end as before and made of a metal suited tothe bath to be treated. In this instance the twyer is inclosed in aprotective sheath of refactory material capable of resisting the actionof the' baths and the temperature at which the operation is performed.This refractory sheath would be firmly secured in place either by ametal collar P at its upper end or otherwise. This construction of twyermay also be employed in the operation before described with reference toFig. 2, it being suited for leading thesodium into the lower part of thebath, especially when it is deep or covered with slag or cinder, uponwhich the sodium is not required to act. It is also equally suitable forbaths'in which the level falls during the incorporation of the sodium,and is particularly useful for the treatment of metals while yetcontained in the producing-furnace before running off. The refractorysheath L protects the twyer from the molten bath and the ambient heat,which would destroy it in course of the operation. It is, however,essential that the end O should remain free and bare in order that itmay become fused on contact with the bath, and thus automatically givepassage to the sodium at the proper moment.

The descriptive details hereinbefore given suflice to enable the actionof the-twyer to be understood. The container C is prepared, put underpressure and in condition for working, as before stated, and is thenbrought into position over the bath and the twyer immersed more or lessdeeply therein, whereupon its point becomes melted off and gives passageto the jet of sodium, which by its vigorous stirring movement becomesdistributed throughout the lower part of the mass in-ne'particlescapable of immediately entering into reaction, as previously described.Y The twyer E,

being protected by the refractory sheath L,` will only be slightlyshortened during the operation, so that it may be applied to act on IOOmetallic baths'in the furnaces themselves or u in ladles of greaterdepth. The twyer of which the end has been burned off should sheath,after each operation.

be either wholly or partly renewed, as also its The bore of the sheathedtwyer may be of increased diameter at its upper part, where the bathdoes not exert any destructive action.

The sodium-container may be made either of cylindrical, spherical,ovoid, or other form, and the compressed gas may bc contained in achamber separate from the sodium-container and be connected thereto by apipe of the necessary strength,` thus forming a two-chamberedapparatus*t The container may be connected to the twyer by means ofelbows, either for the purpose of keeping the vessel C at a distancefrom the ladle, in -which the reaction is performed, or for facilitatingthe adaptation of the apparatus ,to melting-furnaces or other producers,and the axes of thel twyer and vessel C may have different directions,according to circumstances. The pressure applied at F upon the sodiummay be varied at will and within very extended limits without affectingthe principle of the process, which does not depend on any particularpressure, which, however, decreases in consequence of the expansionwhich takes place during the course of the operation. The twyer D, Fig.l, projecting the jet from a distance, requires a higher pressure, whilethe protected twyer E, Fig, 3, even with lower pressure enablespenetration of the sodium to a considerable depth. The pressure shouldnot be below forty-two pounds per square inch, while pressures of twohundred and eightylive pounds, [ive hundred and thirty pounds, or evenseven hundred pounds per square inch and upward are more eiiicacious,especially for the treatment of heavy metals in large masses.

I claiml 1. The herein-described process for the treatment of moltenmatters, which consists in injecting-molten alkali in an attenuated jetinto 'said matters.

2. The herein described process for the treatment of molten matters`which consists in projecting an attenuated jet of moltensodium into suchmatters.

3. The herein described process for the treatment of molten matters,which consists in forcibly introducing liquid material lighter than saidmatters downwardly into such matters.

4. The herein-described process for the treatment of molten matters,which consists in injecting finely-subdivided sodium into the moltenmatter.

5. The herein described process for the treatment of molten matters,which consists in spraying liquid alkaliinto the molten matter.

6. The herein described process for the treatment of molten matterswhich consists in forcibly projecting an attenuated jet of moltenmaterial lighter than said molten 'matters downwardly into such matters.

7 rlhe herein -described process for the treatment of molten matterswhich consists in forcibly projecting an attenuated jet of molten sodiuminto such matters.

8. The herein described process for the treatment of moltenl matterswhich consists in forcibly projecting an attenuated jet of moltenmaterialinto such matters by pressure gener- .atei by the heat appliedto melt said materia 9. The herein described process for the treatmentof molten matters which consists in forcibly projecting an a'ttenuatedljet of molten material into such matters by pressure generated by ahighly-expansible4 substance coniined with said molten material duringthe application of heat 4to melt said material. 10. The herein describedprocess for the treatment of molten matters which consists in forciblyprojecting an attenuated jet of molten lighter material downwardly intosuch matters by pressure generated by a still lighter highly-expansiblesubstance confined with and above said molten material during theapplication of heat to melt said material.

The foregoing specification of my improvements in and in apparatus forthe treatment of metals or matters in fusion with sodium or alkalineAcompounds signed by Ine this 15th day of December, 1902. l'

PAUL LioN HUL'IN W'itncsses:

GAUTIER C. RYoYA F.

